CN109650601A - A kind of Copper making sulfuric acid acid water Zero discharge treatment method - Google Patents

A kind of Copper making sulfuric acid acid water Zero discharge treatment method Download PDF

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CN109650601A
CN109650601A CN201910101506.4A CN201910101506A CN109650601A CN 109650601 A CN109650601 A CN 109650601A CN 201910101506 A CN201910101506 A CN 201910101506A CN 109650601 A CN109650601 A CN 109650601A
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water
arsenic
reverse osmosis
concentrated water
filtrate
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CN109650601B (en
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杜颖
杜冬云
董金兵
陈松
解佑贤
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Hubei Jin Run Moral Green Technology Co Ltd
South Central Minzu University
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Hubei Jin Run Moral Green Technology Co Ltd
South Central University for Nationalities
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F2001/007—Processes including a sedimentation step
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/103—Arsenic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
    • C02F2101/14—Fluorine or fluorine-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/10—Solids, e.g. total solids [TS], total suspended solids [TSS] or volatile solids [VS]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/131—Reverse-osmosis

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  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
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  • Inorganic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

The invention belongs to technical field of industrial sewage treatment, specifically disclose a kind of Copper making sulfuric acid acid water Zero discharge treatment method, it including the following steps: 1, deliming: in sulfuric acid acid water treatment process interlude " be added lime reaction after filtrate " water intaking, by ejector by CO2Mixing is carried out with waste water and adjusts pH to 9.0~9.5, obtains calcium carbonate underflow and filtrate A.2, removing arsenic and fluoride: aluminium salt is added to filtrate A, obtains aluminium salt arsenic slag and liquor B.3, nanofiltration divides salt to be concentrated: carrying out nanofiltration to liquor B and divides salt, obtains sodium sulphate concentrated water and sodium chloride water-dialyzing.4, reverse osmosis concentration: reverse osmosis concentration is carried out to sodium chloride water-dialyzing, obtains sodium chloride concentrated water and water-dialyzing, water-dialyzing can be used as recirculated cooling water moisturizing.5, concentrated water arsenic removal reuse: to reuse after sodium sulphate and the progress arsenic removal of sodium chloride concentrated water.Sulfuric acid acid water is carried out zero discharge treatment by the method for the present invention, invests additional issue crystallization that is low with processing cost, avoiding concentrated water.

Description

A kind of Copper making sulfuric acid acid water Zero discharge treatment method
Technical field
The invention belongs at technical field of industrial sewage treatment more particularly to a kind of Copper making sulfuric acid acid water zero-emission Reason method.
Background technique
China is serious water shortage country, and the one third in the per capita water resource occupation rate deficiency world is horizontal, shortage of water resources Have become the major reason for restricting China's economic development.Under this environmental background, improves water utilization rate and have become the popular feeling Institute is to main trend target.Domestic enterprise also tried to explore zero-discharge technology, low energy consumption, maintenance simple, high service life in recent years Have become the target that enterprise is constantly pursued.Country formulates relevant encouragement guide policy at present, determines pilot, promotes outstanding skill Art provides safeguard for zero discharge of industrial waste water.The promotion efficiency of zero discharge of industrial waste water technology continues to increase.
Copper making industry belongs to typical three Gao Hangye (high pollution, high energy consumption, highly water intensive), and the demand of zero-emission is also got over Come bigger.Wherein for sulfuric acid acid water universally present in coloured industry, it is that maximum one of coloured industry processing difficulty gives up Water.Current most of cupper smeltings use acid water arsenic removal technology, are lime-iron salt methods.Although it is useless after treatment Water can be with qualified discharge, but the waste water of its outlet is because having high rigidity and salinity, fluorine containing arsenic (lower than the outer standard of drainage of country) The characteristics of, lead to its extremely difficult reuse.It is in short supply with water resource, with the rise of water cost, the attention of country and enterprise to environmental protection, The emission reduction or even zero-emission of this part water are particularly important.
On the market the processing technique of zero-emission be using concentrated water evaporative crystallization, but investment cost needed for evaporative crystallization and Processing cost is all very expensive, and enterprise is difficult to receive.Therefore, zero-emission that is how inexpensive, efficiently realizing this one waste water It is very significant.
Summary of the invention
In order to solve the above technical problems in background technology, the present invention provides it is a kind of by sulfuric acid acid water into Row zero discharge treatment, investment and processing cost are low, divide the copper that salt rate is good, producing water ratio is high and can effectively avoid concentrated water additional issue crystallization Smelt sulfuric acid acid water Zero discharge treatment method.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of Copper making sulfuric acid acid water Zero discharge treatment method, includes the following steps:
1) the deliming stage: taking existing sulfuric acid acid water treatment process interlude that the filtrate after lime reaction is added, and leads to Ejector is crossed to mix carbon dioxide gas and filtrate, it is 9.0~9.5 that pH is measured after reaction time 1h, then precipitated, Sand filtration obtains calcium carbonate underflow and filtrate A, and calcium ion concentration is in 1~5mg/L in filtrate A；
Wherein, the filtrate after the addition lime reaction refers to the filtrate after only having added lime medicament to react；
The pH value of filtrate after the addition lime reaction is greater than 12, and calcium ion content is in 600~800mg/L, arsenic element Content is in 1~20mg/L, and fluorine element content is in 10~80mg/L, and TDS is in 10~20g/L；
Gasification of the carbon dioxide gas from liquid carbon dioxide；Ejector is a preparation and a use, works as carbon dioxide gas When partial pressure is greater than or equal to 0.1MPa, ejector is represented there are stopping state, needs to carry out pickling to ejector；Carbon dioxide Utilization rate is 90% or more；
The calcium carbonate underflow may be used as front end sulfuric acid acid water treatment agent；
2) the removing arsenic and fluoride stage: aluminum sulfate solution or liquor alumini chloridi being added into filtrate A obtained by step 1), carry out removing arsenic and fluoride Then reaction carries out two-stage and adds acid for adjusting pH (two-stage refers to acid adding in two times), the pH value that two-stage is adjusted is respectively 7.0~8.0 Hes 6.0~7.0.It is precipitated after reaction to stabilization, sand filtration, obtains aluminium salt arsenic slag and liquor B；
Aluminum sulfate or liquor alumini chloridi are 10wt% aqueous solution；
The amount MAl of the substance of aluminium be added3+, the amount MF of it and the substance of fluorine in filtrate A-Between relationship be MAl3+= MF-；
Two-stage add acid used when acid for adjusting pH be mass fraction be 40-60% sulfuric acid, preferably 50%；
The removal rate of arsenic is greater than 50% in step 2), and the removal rate of fluorine is not less than 80%.Fluorine contains in liquor B obtained by step 2) Amount is in 1~10mg/L, and arsenic content is in 1~10mg/L, and TDS is in 8~17g/L；In step 2) aluminium salt arsenic slag the content of arsenic 1~ Between 4%, the leaching concentration of arsenic is less than 1mg/L；
3) nanofiltration divides salt enriching stage: liquor B passes through core type filter (model used in following example 1-3 CFH7-10 after), two sections of nanofiltrations is successively carried out and divide salt (pressure is respectively 2.1-2.6MPa and 3.6-4.2MPa), two sections of nanofiltrations It intakes after water-dialyzing mixing afterwards as reverse osmosis film.Concentrated water after first segment nanofiltration passes through 50wt% sulphur acid for adjusting pH value After 5.0~6.0, adding hydrolysis of polymaleic anhydride, (the dosing dosage of hydrolysis of polymaleic anhydride is 5~10mg/L, i.e. every liter of water It is middle that 5~10mg hydrolysis of polymaleic anhydride is added) water inlet as second segment nanofiltration, concentrated water obtained by second segment nanofiltration is dense for sodium sulphate Water.After two sections of nanofiltrations, comprehensive producing water ratio is 90% or so, and 96% or more, the transmitance of chlorine root exists the salt rejection rate of sulfate radical 96% or more；
The first segment nanofiltration cycles of concentration is 4.5-5.5 times, and second segment nanofiltration cycles of concentration is 1.5-2.5 times；
4) the reverse osmosis concentration stage: the water-dialyzing after dividing step 3) nanofiltration salt successively carries out three sections of reverse osmosis (pressure point Wei 2.1-2.5MPa, 3.6-4.1MPa and 6.9-8.0MPa), the reverse osmosis concentrated water of first segment is reverse osmosis as second segment Water inlet, the water inlet reverse osmosis as third section of second segment reverse osmosis concentrated water.The reverse osmosis water-dialyzing of the third level is anti-as first segment The water inlet of infiltration, the reverse osmosis concentrated water of third section are sodium chloride concentrated water.As circulation after first two sections reverse osmosis water-dialyzing mixing Cooling water replenishment.After three sections of reverse osmosis concentrations, comprehensive producing water ratio is 95% or more, and salt rejection rate is 97% or more；Two before step 4) Meet circulating cooling in " Code for design of industrial recirculating cooling water treatment " (GB/T50050-017) after the reverse osmosis water-dialyzing mixing of section Water moisturizing standard；
The first segment reverse osmosis concentration multiple is 3.5-4.5 times, and second segment reverse osmosis concentration multiple is 2.5-3.5 times, The reverse osmosis cycles of concentration of third section is 2.5-3.5 times；5) concentrated water arsenic removal reuse: the sulphur that step 3) and step 4) are generated respectively Sour sodium concentrated water, sodium chloride concentrated water carry out the arsenic removal of interval list type using molysite, each reuse point reuse are respectively enterd after arsenic removal；
The medicament that sodium sulphate concentrated water arsenic removal uses reacts pH 8.0~9.0, iron arsenic molar ratio exists for ferric sulfate and liquid alkaline 10~13；
The medicament that sodium chloride concentrated water arsenic removal uses reacts pH 8.0~9.0, iron arsenic molar ratio exists for iron chloride and liquid alkaline 10~13；
Sodium sulphate concentrated water and sodium chloride concentrated water TDS after arsenic removal is in 90g/L or so；
The reaction step of the interval list type arsenic removal is followed successively by into water, surveys arsenic, addition molysite medicament, addition liquid alkaline adjusting PH, precipitating filtering；2-3 reaction tank is successively alternately.
Reuse to concentrate store is humidified after the sodium sulphate concentrated water arsenic removal；
Reuse to rare precious metal purifies after the sodium chloride concentrated water arsenic removal；
The content of arsenic is respectively less than 0.5mg/L in filtrate after two concentrated water arsenic removals in step 5)；Two concentrated water arsenic removal in step 5) The content of arsenic is less than 1mg/L in the leaching concentration of 1~3% and arsenic in molysite arsenic slag after filter；
The molysite arsenic slag that the aluminium salt arsenic slag of step 2) and step 5) concentrated water arsenic removal generate be required to do after curing process again into Row security landfill.
Compared with prior art, the processing method of sulfuric acid acid water zero-emission of the invention has the advantages that
1, it fetches water in sulfuric acid acid water interlude, reduces original processing cost:
The traditional processing method of sulfuric acid waste acid is first to be removed arsenic to 20mg/L hereinafter, again with molysite to remaining with lime Arsenic is removed, and the concentration of arsenic is made to be reduced to 0.5mg/L or less.The medicament expense of this part molysite accounts for original medicament operating cost 1/3.By this method in " filtrate after lime reaction is added " water intaking, the addition of molysite is eliminated, arsenic removal process 1/3 is reduced Processing cost provides preferable economic condition for sulfuric acid acid water zero-emission.A large amount of molysite medicament in the prior art simultaneously Addition, will increase salinity in waste water, to reduce the producing water ratio of film.
2, carbon dioxide deliming processing cost is low, high treating effect: in the present invention, by ejector by carbon dioxide and useless Water is mixed, and the utilization rate of carbon dioxide can be substantially improved, and compared with sodium carbonate is except hardness, processing cost is the latter's 1/4.Carbon dioxide can not only remove the calcium ion in waste water simultaneously (calcium ion removal rate is 99% or more), moreover it is possible to reduce useless The pH value of water reduces the addition of dilute sulfuric acid in second step removing arsenic and fluoride, reduces the addition of the additional salinity of system.
3, producing water ratio is high, system is stable, processing cost is low: the producing water ratio of the method for the present invention is up to 85% or more, main The reason is as follows that: 1. by carbon dioxide deliming and aluminium salt removing arsenic and fluoride, not only without the salinity of increase waste water, waste water 10 is reduced instead ~20% salinity provides preferable precondition to increase the producing water ratio of film；2. carbon dioxide except hardness it is minimum can by waste water calcium from Sub- concentration is reduced to 1mg/L, provides solid foundation for the high power concentration of waste water；3. being concentrated using two sections of points of salt of nanofiltration and reverse osmosis Three sections of concentrations can reduce processing cost to the maximum extent and improve producing water ratio.After dividing salt and reverse osmosis concentration by nanofiltration, obtain Sodium sulphate concentrated water and sodium chloride concentrated water are arrived, concentrated water water is only 15% or so of original place reason water, using intermittent sequence Arsenic removal can increase the stability of system arsenic removal.The resource utilization of two bursts of concentrated waters, avoid evaporative crystallization great number investment and Operating cost also avoids the storage and disposition of crystal salt.Compared with traditional technique of zero discharge, the processing waste water of the method for the present invention Extraneous expense expense is only the former 60%.
Detailed description of the invention
Fig. 1 is a kind of basic procedure schematic diagram of Copper making sulfuric acid acid water Zero discharge treatment method of the invention.
Specific embodiment
Below by taking specific embodiment as an example, technical solution provided by the present invention is described in detail:
Referring to Fig. 1, the present invention provides a kind of Copper making sulfuric acid acid water Zero discharge treatment method, (embodiment 1-3 is equal Implement documented by step in accordance with the following methods), this method comprises the following steps:
1) the deliming stage: taking original sulfuric acid acid water treatment process interlude that the filtrate after lime reaction is added, and leads to Ejector is crossed to mix carbon dioxide gas and filtrate, it is 9.0~9.5 that pH is measured after reaction time 1h, then precipitated, Sand filtration obtains calcium carbonate underflow and filtrate A, and calcium ion concentration is in 1~5mg/L in filtrate A；
Wherein, the filtrate after the addition lime reaction refers to the filtrate after only having added lime medicament to react；
The pH value of filtrate after the addition lime reaction is greater than 12, and calcium ion content is in 600~800mg/L, arsenic element Content is in 1~20mg/L, and fluorine element content is in 10~80mg/L, and TDS is in 10~20g/L；
Gasification of the carbon dioxide gas from liquid carbon dioxide；Ejector is a preparation and a use, works as carbon dioxide gas When partial pressure is greater than or equal to 0.1MPa, ejector is represented there are stopping state, needs to carry out pickling to ejector；Carbon dioxide Utilization rate is 90% or more；
The calcium carbonate underflow may be used as front end sulfuric acid acid water treatment agent；
2) the removing arsenic and fluoride stage: aluminum sulfate solution or liquor alumini chloridi being added into filtrate A obtained by step 1), carry out removing arsenic and fluoride Then reaction carries out two-stage and adds acid for adjusting pH (two-stage refers to acid adding in two times), the pH value that two-stage is adjusted is respectively 7.0~8.0 Hes 6.0~7.0.It is precipitated after reaction to stabilization, sand filtration, obtains aluminium salt arsenic slag and liquor B；
Aluminum sulfate or liquor alumini chloridi are 10wt% aqueous solution；
The amount MAl of the substance of aluminium be added3+, the amount MF of it and the substance of fluorine in filtrate A-Between relationship be MAl3+= MF-；
Two-stage adds acid used when acid for adjusting pH to be the sulfuric acid that mass fraction is 50%；
The removal rate of arsenic is greater than 50% in step 2), and the removal rate of fluorine is not less than 80%.Fluorine contains in liquor B obtained by step 2) Amount is in 1~10mg/L, and arsenic content is in 1~10mg/L, and TDS is in 8~17g/L；In step 2) aluminium salt arsenic slag the content of arsenic 1~ Between 4%, the leaching concentration of arsenic is less than 1mg/L；
3) nanofiltration divides salt enriching stage: liquor B passes through core type filter (model used in following example 1-3 CFH7-10 after), two sections of nanofiltrations is successively carried out and divide salt (pressure is respectively 2.1-2.6MPa and 3.6-4.2MPa), two sections of nanofiltrations It intakes after water-dialyzing mixing afterwards as reverse osmosis film.Concentrated water after first segment nanofiltration passes through 50wt% sulphur acid for adjusting pH value After 5.0~6.0, adding hydrolysis of polymaleic anhydride, (the dosing dosage of hydrolysis of polymaleic anhydride is 5~10mg/L, i.e. every liter of water Middle addition 5~10mg hydrolysis of polymaleic anhydride, the relative molecular weight of hydrolysis of polymaleic anhydride are 400-800) it is received as second segment The water inlet of filter, second segment nanofiltration gained concentrated water is sodium sulphate concentrated water.After two sections of nanofiltrations, comprehensive producing water ratio is 90% or so, sulfuric acid The salt rejection rate of root is 96% or more, and the transmitance of chlorine root is 96% or more；
The first segment nanofiltration cycles of concentration is 4.5-5.5 times, and second segment nanofiltration cycles of concentration is 1.5-2.5 times；
4) the reverse osmosis concentration stage: the water-dialyzing after dividing step 3) nanofiltration salt successively carries out three sections of reverse osmosis (pressure point Wei 2.1-2.5MPa, 3.6-4.1MPa and 6.9-8.0MPa), the reverse osmosis concentrated water of first segment is reverse osmosis as second segment Water inlet, the water inlet reverse osmosis as third section of second segment reverse osmosis concentrated water.The reverse osmosis water-dialyzing of the third level is anti-as first segment The water inlet of infiltration, the reverse osmosis concentrated water of third section are sodium chloride concentrated water.As circulation after first two sections reverse osmosis water-dialyzing mixing Cooling water replenishment.After three sections of reverse osmosis concentrations, comprehensive producing water ratio is 95% or more, and salt rejection rate is 97% or more；Two before step 4) Meet circulating cooling in " Code for design of industrial recirculating cooling water treatment " (GB/T50050-017) after the reverse osmosis water-dialyzing mixing of section Water moisturizing standard；
The first segment reverse osmosis concentration multiple is 3.5-4.5 times, and second segment reverse osmosis concentration multiple is 2.5-3.5 times, The reverse osmosis cycles of concentration of third section is 2.5-3.5 times；5) concentrated water arsenic removal reuse: the sulphur that step 3) and step 4) are generated respectively Sour sodium concentrated water, sodium chloride concentrated water carry out the arsenic removal of interval list type using molysite, each reuse point reuse are respectively enterd after arsenic removal；
The medicament that sodium sulphate concentrated water arsenic removal uses reacts pH 8.0~9.0, iron arsenic molar ratio exists for ferric sulfate and liquid alkaline 10~13；
The medicament that sodium chloride concentrated water arsenic removal uses reacts pH 8.0~9.0, iron arsenic molar ratio exists for iron chloride and liquid alkaline 10~13；
Sodium sulphate concentrated water and sodium chloride concentrated water TDS after arsenic removal is in 90g/L or so；
The reaction step of the interval list type arsenic removal is followed successively by into water, surveys arsenic, addition molysite medicament, addition liquid alkaline adjusting PH, precipitating filtering；2-3 reaction tank is successively alternately.
Reuse to concentrate store is humidified after the sodium sulphate concentrated water arsenic removal；
Reuse to rare precious metal purifies after the sodium chloride concentrated water arsenic removal；
The content of arsenic is respectively less than 0.5mg/L in filtrate after two concentrated water arsenic removals in step 5)；Two concentrated water arsenic removal in step 5) The content of arsenic is less than 1mg/L in the leaching concentration of 1~3% and arsenic in molysite arsenic slag after filter；
The molysite arsenic slag that the aluminium salt arsenic slag of step 2) and step 5) concentrated water arsenic removal generate be required to do after curing process again into Row security landfill.
Illustrate the performance and technical effect of the above specific embodiment with three specific embodiments below.
Liquid alkaline mass fraction used is 30% in following embodiment, and nanofiltration membrane and reverse osmosis membrane are aromatic polyamide Film.
Embodiment 1
The present embodiment is with the original sulfuric acid acid water of sulfuric acid acid water that Hubei copper smelting plant sulfuric acid plant is discharged Treatment process interlude " filtrate after lime reaction is added " is to deal with objects, pH value 12.5, and calcium ion concentration is 680mg/L, arsenic content 15mg/L, fluorine content 20mg/L, TDS 16g/L.
Sulfuric acid acid water Zero discharge treatment method described in a kind of the present embodiment, its step are as follows:
1) the deliming stage: the filtrate 0.5m after lime reaction is added is taken3, carbon dioxide gas flow is 215L (1atm Under), pH value is 9.1 after reacting 1h, then is precipitated, sand filtration, and filtrate A is obtained；
Calcium ion concentration is 2mg/L, arsenic content 15mg/L in filtrate after sand filtration, and fluorine content 20mg/L, TDS are 14g/L；
2) the removing arsenic and fluoride stage: being added 0.9L aluminum sulfate solution (10wt%) into filtrate A, after two-stage adjusts pH value (pH is respectively 7.1 and 6.2), is precipitated, sand filtration, and liquor B and aluminium salt arsenic slag are obtained；Calcium ion concentration is 2mg/ in liquor B L, arsenic content 5mg/L, fluorine content 4mg/L, TDS 14g/L；
For the content of arsenic 1.6%, the leaching concentration of arsenic is 0.3mg/L in aluminium salt arsenic slag；
3) nanofiltration divides salt phase: for liquor B after core type filter, first segment nanofiltration pressure is 2.5MPa, uses 50wt% First segment nanofiltration concentrated water is adjusted pH to 5.5 by sulfuric acid, and the hydrolysis of polymaleic anhydride that 6mg/L (dosing dosage, similarly hereinafter) is added is laggard Enter second segment nanofiltration and divide salt, second segment nanofiltration pressure is 3.7Mpa；
Nanofiltration divides the total producing water ratio of salt to be 87.5%, and sulfate radical salt rejection rate is 97.2%, and chlorine root transmitance is 98.4%；Second Calcium ion concentration is 16mg/L, arsenic content 30mg/L, fluorine content 4mg/L, TDS 90g/L in section nanofiltration concentrated water；First segment Calcium ion is not detected in solution after mixing with second segment nanofiltration water-dialyzing, arsenic content 1.4mg/L, fluorine content 4mg/L, TDS For 3.1g/L；
Continuous service two weeks, film does not occur blocking the phenomenon that causing producing water ratio to decline because of film, if 50wt% sulphur is not added There is film clogging after then running 1 day in acid for adjusting pH value and hydrolysis of polymaleic anhydride；
4) reverse osmosis concentration: to nanofiltration water-dialyzing carry out three sections it is reverse osmosis (pressure be respectively 2.3MPa, 3.8MPa, 7.2MPa)；Reverse osmosis total producing water ratio is 96.6%, salt rejection rate 97.5%；Arsenic content is 42mg/ in third section reverse osmosis concentrated water L, fluorine content 110mg/L, TDS 90g/L；" industrial cycle is cold for satisfaction after first segment and the reverse osmosis water-dialyzing mixing of second segment But water process design specification " recirculated cooling water moisturizing standard in (GB/T50050-017)；
5) concentrated water arsenic removal: being added ferrum sulfuricum oxydatum solutum (10wt%) into nanofiltration concentrated water, and iron arsenic molar ratio is 10, with liquid alkaline tune After saving pH value 8.5, precipitating is filtered, and arsenic content is 0.1mg/L in filtrate, and filtrate is sent to concentrate store and is humidified, arsenic in molysite arsenic slag Content is 0.1mg/L in the leaching concentration of 2.4% and arsenic；Ferric chloride solution (10wt%) is added into reverse osmosis concentrated water, iron arsenic Molar ratio is 10, and after adjusting pH value 8.5 with liquid alkaline, precipitating is filtered, and arsenic content is 0.2mg/L in filtrate, and filtrate is used for your dilute gold Belong to and extracting, the content of arsenic is 0.1mg/L in the leaching concentration of 2.5% and arsenic in molysite arsenic slag.
Embodiment 2
The present embodiment is with the original sulfuric acid acid water of sulfuric acid acid water that Gansu copper smelting plant sulfuric acid plant is discharged Treatment process interlude " filtrate after lime reaction is added " is to deal with objects, pH value 12.2, and calcium ion concentration is 600mg/L, arsenic content 5mg/L, fluorine content 40mg/L, TDS 11g/L.
Zero discharge treatment method in sulfuric acid waste acid described in a kind of the present embodiment, its step are as follows:
1) the deliming stage: the filtrate 0.5m after lime reaction is added is taken3, carbon dioxide gas flow is 180L (1atm Under), pH value is 9.3 after reacting 1h, then is precipitated, sand filtration, and filtrate A is obtained；
Calcium ion concentration is 5mg/L, arsenic content 5mg/L in filtrate after sand filtration, and fluorine content 40mg/L, TDS are 8.8g/L；
2) the removing arsenic and fluoride stage: being added 1.8L aluminum sulfate solution (10wt%) into filtrate A, after two-stage adjusts pH value (pH is respectively 7.5 and 6.5), is precipitated, sand filtration, and liquor B and aluminium salt arsenic slag are obtained；Calcium ion concentration is 5mg/ in liquor B L, arsenic content 2.5mg/L, fluorine content 7mg/L, TDS 8.8g/L；
For the content of arsenic 1.2%, the leaching concentration of arsenic is 0.1mg/L in aluminium salt arsenic slag；
3) nanofiltration divides salt phase: for liquor B after core type filter, first segment nanofiltration pressure is 2.2MPa, uses 50wt% First segment nanofiltration concentrated water is adjusted pH to 5.7 by sulfuric acid, enters second segment nanofiltration point after the hydrolysis of polymaleic anhydride of 7mg/L is added Salt, second segment nanofiltration pressure are 3.8Mpa；
Nanofiltration divides the total producing water ratio of salt to be 93%, and sulfate radical salt rejection rate is 96.2%, and chlorine root transmitance is 99.4%；Second segment Calcium ion concentration is 28mg/L, arsenic content 8mg/L, fluorine content 7mg/L, TDS 89g/L in nanofiltration concentrated water；First segment and Middle calcium ion is not detected after the mixing of second segment nanofiltration water-dialyzing, arsenic content 2.1mg/L, fluorine content 7mg/L, TDS 2.5g/ L；
Continuous service two weeks film does not occur blocking the phenomenon that causing producing water ratio to decline because of film, if 50wt% sulfuric acid is not added PH value and hydrolysis of polymaleic anhydride are adjusted, then film clogging occurs after running 1 day；
4) reverse osmosis concentration: to nanofiltration water-dialyzing carry out three sections it is reverse osmosis (pressure be respectively 2.2MPa, 3.7MPa, 7.0MPa)；Reverse osmosis total producing water ratio is 97.4%, salt rejection rate 97.4%；Arsenic content is 73mg/ in third section reverse osmosis concentrated water L, fluorine content 230mg/L, TDS 85g/L；" industrial cycle is cold for satisfaction after first segment and the reverse osmosis water-dialyzing mixing of second segment But water process design specification " recirculated cooling water moisturizing standard in (GB/T50050-017)；
5) concentrated water arsenic removal: being added ferrum sulfuricum oxydatum solutum (10wt%) into nanofiltration concentrated water, and iron arsenic molar ratio is 11, with liquid alkaline tune After saving pH value 9.0, precipitating is filtered, and arsenic content is 0.1mg/L in filtrate, and filtrate is sent to concentrate store and is humidified, arsenic in molysite arsenic slag Content is 0.1mg/L in the leaching concentration of 1.5% and arsenic；Ferric chloride solution (10wt%) is added into reverse osmosis concentrated water, iron arsenic Molar ratio is 11, and after adjusting pH value 9.0 with liquid alkaline, precipitating is filtered, and arsenic content is 0.3mg/L in filtrate, and filtrate is used for your dilute gold Belong to and extracting, the content of arsenic is 0.1mg/L in the leaching concentration of 2.1% and arsenic in molysite arsenic slag.
Embodiment 3
The present embodiment is with the original sulfuric acid acid water of sulfuric acid acid water that Anhui copper smelting plant sulfuric acid plant is discharged Treatment process interlude " filtrate after lime reaction is added " is to deal with objects, pH value 13.0, and calcium ion concentration is 800mg/L, arsenic content 20mg/L, fluorine content 75mg/L, TDS 19g/L.
Sulfuric acid acid water Zero discharge treatment method described in a kind of the present embodiment, its step are as follows:
1) the deliming stage: the filtrate 0.5m after lime reaction is added is taken3, carbon dioxide gas flow is 250L (1atm Under), pH value is 9.5 after reacting 1h, then is precipitated, sand filtration, and filtrate A is obtained；Calcium ion concentration is in filtrate after sand filtration 1mg/L, arsenic content 20mg/L, fluorine content 75mg/L, TDS 16g/L；
2) the removing arsenic and fluoride stage: being added 3.3L aluminum sulfate solution (10wt%) into filtrate A, after two-stage adjusts pH value (pH is respectively 7.7 and 6.8), is precipitated, sand filtration, and liquor B and aluminium salt arsenic slag are obtained；Calcium ion concentration is 1mg/ in liquor B L, arsenic content 8mg/L, fluorine content 8mg/L, TDS 16g/L；
For the content of arsenic 1.3%, the leaching concentration of arsenic is 0.2mg/L in aluminium salt arsenic slag；
3) nanofiltration divides salt phase: for liquor B after core type filter, first segment nanofiltration pressure is 2.5MPa, and use is dilute First segment nanofiltration concentrated water is adjusted pH to 5.2 by 50wt% sulfuric acid, is received after the hydrolysis of polymaleic anhydride of 9mg/L is added into second segment Filter divides salt, and second segment nanofiltration pressure is 4.0Mpa；Nanofiltration producing water ratio is 87%, and sulfate radical salt rejection rate is 97.8%, and chlorine root penetrates Rate is 97.9%；In second segment nanofiltration concentrated water calcium ion concentration be 10mg/L, arsenic content 45mg/L, fluorine content 8mg/L, TDS is 95g/L；Middle calcium ion is not detected after first segment and the mixing of second segment nanofiltration water-dialyzing, and arsenic content 4.4mg/L, fluorine contains Amount is 4mg/L, TDS 3.5g/L；
Continuous service two weeks film does not occur blocking the phenomenon that causing producing water ratio to decline because of film, if 50wt% sulfuric acid is not added PH value and hydrolysis of polymaleic anhydride are adjusted, then film clogging occurs after running 1 day；
4) reverse osmosis concentration: to nanofiltration water-dialyzing carry out three sections it is reverse osmosis (pressure be respectively 2.4MPa, 4.0MPa, 7.5MPa)；Reverse osmosis total producing water ratio is 97.1%, salt rejection rate 97.2%；Arsenic content is 73mg/ in third section reverse osmosis concentrated water L, fluorine content 130mg/L, TDS 90g/L；" industrial cycle is cold for satisfaction after first segment and the reverse osmosis water-dialyzing mixing of second segment But water process design specification " recirculated cooling water moisturizing standard in (GB/T50050-017)；
5) concentrated water arsenic removal: being added ferrum sulfuricum oxydatum solutum (10wt%) into nanofiltration concentrated water, and iron arsenic molar ratio is 12, with liquid alkaline tune After saving pH value 8.5, precipitating is filtered, and arsenic content is 0.3mg/L in filtrate, and filtrate is sent to concentrate store and is humidified, arsenic in molysite arsenic slag Content is 0.1mg/L in the leaching concentration of 2.5% and arsenic；Ferric chloride solution (10wt%) is added into reverse osmosis concentrated water, iron arsenic Molar ratio is 12, and after adjusting pH value 8.5 with liquid alkaline, precipitating is filtered, and arsenic content is 0.4mg/L in filtrate, and filtrate is used for your dilute gold Belong to and extracting, the content of arsenic is 0.1mg/L in the leaching concentration of 2.1% and arsenic in molysite arsenic slag.

Claims (8)

1. a kind of Copper making sulfuric acid acid water Zero discharge treatment method, includes the following steps:
1) the deliming stage: taking sulfuric acid acid water treatment process interlude that the filtrate after lime reaction is added, will by ejector Carbon dioxide gas and filtrate are mixed, and it is 9.0~9.5 that pH is measured after reaction, then is precipitated, sand filtration, obtain calcium carbonate Underflow and filtrate A, calcium ion concentration is in 1~5mg/L in filtrate A；
2) the removing arsenic and fluoride stage: aluminum sulfate solution or liquor alumini chloridi being added into filtrate A obtained by step 1), and it is anti-to carry out removing arsenic and fluoride It answers, then carries out two-stage and add acid for adjusting pH, the pH value that two-stage is adjusted is respectively 7.0~8.0 and 6.0~7.0, after reaction to stabilization It is precipitated, sand filtration, obtains aluminium salt arsenic slag and liquor B；
3) nanofiltration divides salt enriching stage: liquor B successively carries out two sections of nanofiltrations and divides salt, after two sections of nanofiltrations after core type filter Water-dialyzing mixing after intake as reverse osmosis film, the concentrated water after first segment nanofiltration through persulfuric acid adjust pH value for 5.0~ 6.0, the water inlet after 5~10mg/L hydrolysis of polymaleic anhydride as second segment nanofiltration is added, concentrated water obtained by second segment nanofiltration is Sodium sulphate concentrated water；
Two sections of nanofiltration pressures are followed successively by 2.1-2.6MPa and 3.6-4.2MPa；
4) the reverse osmosis concentration stage: the water-dialyzing after dividing step 3) nanofiltration salt successively carries out three sections of reverse osmosis, first segment reverse osmosis The water inlet reverse osmosis as second segment of saturating concentrated water, the water inlet reverse osmosis as third section of second segment reverse osmosis concentrated water, the third level The water inlet reverse osmosis as first segment of reverse osmosis water-dialyzing, the reverse osmosis concentrated water of third section are sodium chloride concentrated water, and first two sections anti- Recirculated cooling water moisturizing is used as after the water-dialyzing mixing of infiltration；
Three sections of reverse osmosis pressure is followed successively by 2.1-2.5MPa, 3.6-4.1MPa and 6.9-8.0MPa；
5) concentrated water arsenic removal reuse: sodium sulphate concentrated water, the sodium chloride concentrated water that step 3) and step 4) are generated respectively, using molysite into It in the ranks has a rest list type arsenic removal, each reuse point reuse is respectively enterd after arsenic removal；
The medicament that sodium sulphate concentrated water arsenic removal uses is ferric sulfate and liquid alkaline, and pH is 8.0~9.0 for reaction, iron arsenic molar ratio 10~ 13；
The medicament that sodium chloride concentrated water arsenic removal uses is iron chloride and liquid alkaline, and pH is 8.0~9.0 for reaction, iron arsenic molar ratio 10~ 13；
The reaction step of the interval list type arsenic removal be followed successively by into water, survey arsenic, be added molysite medicament, be added liquid alkaline adjust pH, Precipitating filtering；
The molysite arsenic slag that the aluminium salt arsenic slag of step 2) and step 5) concentrated water arsenic removal generate carries out security landfill after doing curing process again.
2. processing method according to claim 1, it is characterised in that: the pH value of the filtrate being added after lime reaction is big In 12, calcium ion content in 600~800mg/L, arsenogen cellulose content in 1~20mg/L, fluorine element content in 10~80mg/L, TDS is in 10~20g/L.
3. processing method according to claim 1, it is characterised in that: the calcium carbonate underflow is useless as front end sulfuric acid waste acid Water treatment agent.
4. processing method according to claim 2 or 3, it is characterised in that: the first segment nanofiltration cycles of concentration is 4.5- 5.5 times, second segment nanofiltration cycles of concentration is 1.5-2.5 times.
5. processing method according to claim 2 or 3, it is characterised in that: the first segment reverse osmosis concentration multiple is 3.5-4.5 times, second segment reverse osmosis concentration multiple is 2.5-3.5 times, and the reverse osmosis cycles of concentration of third section is 2.5-3.5 times.
6. processing method according to claim 1, it is characterised in that: the amount of the substance of aluminium be added in the step 2) MAl3+, the amount MF of it and the substance of fluorine in filtrate A-Between relationship be MAl3+=MF-。
7. processing method according to claim 1, it is characterised in that: reuse is to concentrate store after the sodium sulphate concentrated water arsenic removal Humidification.
8. processing method according to claim 1, it is characterised in that: reuse is to your dilute gold after the sodium chloride concentrated water arsenic removal Belong to purification.
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